Professional Documents
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• The Problem
– Diminishing supply?
– Resources in unfriendly locations?
– Environmental damage?
• The Solution
– Adequate domestic supply
– Environmentally benign
– Conveniently transported
– Conveniently used
106 3.3
52 1.7
0 0
2.0E+05
Rsv = Reserves (90%)
Rsc = Resources (50%)
1.5E+05
(Exa)J
1.0E+05
Unconv
Conv
5.0E+04
0.0E+00
Oil Oil Gas Gas Coal Coal
Rsv Rsc Rsv Rsc Rsv Rsc
Source Reserves, yrs Resources, yrs Total, yrs
Oil 13 - 20 10 – 35 23 - 55
56-77 287-345
Towards a Sustainable Energy Future
US Energy Imports/Exports: 1949-2004
Source: US Energy Information Agency
35
Imports Exports
6
30 Total
5
25
Quad BTU
Total 4
Quad BTU
20 Coal
3
15
10 2
Petroleum
5 1 Petroleum
0 0
1950 1960 1970 1980 1990 2000 1950 1960 1970 1980 1990 2000
20
15 1957: Net Importer
10
5
0
330
Projections:
320 500-700 ppm by 2020
310
• Anthropogenic Industrial
300 – Fossil fuel (75%) Revolution
– Land use (25%)
290
280
270
1000 1200 1400 1600 1800 2000
Source: Oak Ridge National Laboratory year
Towards a Sustainable Energy Future
Environmental Outlook
T relative to
300 700
present (°C)
-- T 0
275
600
250
500 -4
225
200 400 -8
175 300
400 300 200 100 0
Thousands of years before present (Ky BP)
Urgency
• Transport of CO2 or heat into deep oceans:
– 400-1000 years; CO2 build-up is cummulative
• Must make dramatic changes within next few years
Wind Biomass
2-4 TW extractable 5-7 TW gross
all cultivatable
land not used
Tide/Ocean for food
Currents
2 TW gross
Hydroelectric
Geothermal 4.6 TW gross
12 TW gross over land 1.6 TW technically feasible
small fraction recoverable 0.9 TW economically feasible
0.6 TW installed capacity
Nuclear
Waste disposal Fossil with sequestration
1% / yr leakage -> lost in 100 yrs
Solar or nuclear
Capture e- power plants
H2
???
Batteries Hydrides?
Storage Hydrocarbon Liquid H2?
Delivery
e-
Utilization H2O + CO2
Fuel cell
Towards a Sustainable Energy Future
A Few Words on Hydrogen Fuel Cells
• High efficiency
automotive engine: 50-75 kW – low CO2 emissions
80
• Size independent
efficiency [%]
60
* • Various applications
40 – stationary
– automotive
20 – portable electronics
• Controlled reactions
0
0 5 10 15 20 25 – “Zero Emissions”
power plant size [MW] • Operable on hydrogen
– (if suitably produced)
e-
H+
H2 O2
H2 2H+ + 2e- ½ O2 + 2H+ + 2e- H2O
Electrolyte
Overall: H2 + ½ O2 H2O
Towards a Sustainable Energy Future
Fuel Cell Performance
H2 + ½ O2 H2O
1.2 0.8
1.17 Volts (@ no current) cross-over theoretical voltage
1.0
slow reaction kinetics
0.6
• voltage losses
Power [W / cm2]
0.8 peak power
Voltage [V]
– fuel cross-over
0.6 0.4
– reaction kinetics
– electrolyte resistance 0.4 electrolyte
resistance 0.2
– slow mass diffusion 0.2
slow mass
• power = I*V diffusion
0.0 0.0
• peak efficiency at low I 0.0 0.4 0.8 1.2 1.6
Current [A / cm2 ]
• peak power at mid I
– Electrolyte (Membrane)
• Transport ions
• Block electrons, gases
– Electrodes
• Catalyze reactions
• Transport
– Ions, electrons, gases
• May be a composite sealant
– (electro)Catalyst + electrolyte
– Conductors +
– Pore former Membrane-Electrode
Assembly (MEA)
Towards a Sustainable Energy Future
Fuel Cell Types
Fuel H2 + H2O H2 H2 HC + CO HC + CO
• Applications • Applications
– Portable power – Stationary power
– Many on/off cycles – Auxiliary power in
– Small size portable systems
electrodes catalyst
Electrolyte
System
Stack
Challenge
• Limitation of fuel cell materials places severe
design constraints on fuel cell systems
Approach
• Material modification for improved performance
and system simplification
• New materials discovery for next generation
fuel cell systems
• Novel system designs
• New Electrolytes
– Intermediate temperature operation
• Lower the temperature below solid oxide fuel cells
• Raise the temperature above polymer fuel cells
• New Catalysts
– Enhance reaction kinetics (improve efficiency)
– Reduce susceptibility to poisons (reduce complexity)
• Novel integrated designs
– Dramatically improve thermal management
– Utilize micromachining technologies – micro fuel cells
H(H2O)n+
Nafion (Dupont)
H2O
• saturate with H2O
SO3- + (H2O)nH+
– inverse micelle structure
1 nm
• H(H2O)n+ ion transport
(CF2)n
High conductivity
Flexible, high strength
Requires humidification &
water management
Operation below 90°C
Permeable to methanol
Kreuer, J Membr Sci 2 (2001) 185.
• Chemical intermediates
between normal salts and d is o r d e r e d
normal acids: “acid salts” s tru c tu re p o ly m e r
lo g ( c o n d u c t iv it y )
½(Cs2SO4) + ½(H2SO4) CsHSO4
H
Sulfate group
reorientation
S
O 10-11 seconds
Proton transfer
10-9 seconds
log(conductivity) [S / cm]
• (NH4)3H(SO4)2
[Ramasastry, 1981] -3
• Rb3H(SeO4)2
-4
[Pawlowski, 1988]
• Cs2(HSO4)(H2PO4) -5
• K3H(SO4)2 -8
[Chisholm & Haile, 2001] 2.00 2.25 2.50 2.75 3.00 3.25
-1
1000/T K
Water temperature ( C)
Equilibrium pH O(atm)
CsH2PO4 + H2O
o
0.3 P(H2O) operation
71
4
PO
0.2
4-x
62
PO
2
H
Cs
x
0.1
2-2
47
H
Cs
0.0
200 225 250 275 300
Temperature(C)
2nd heating
-1
2nd cooling
-1
Humidified air
p[H2O] = 0.4 atm
-4
-6 230 °C
40
power High open circuit voltage
0.6
30
– Theoretical: 1.15V
0.4 20 – Measured: 1.00 V
voltage – Polymers: 0.8-0.9 V
0.2 10
Power density
0.0 0
– Polymers: > 1 W/cm2
0 50 100 150 200 250 300
Current density (mA cm )
-2 • Platinum content
– Polymers: ~ 0.1 mg/cm2
260m membrane; 18 mg Pt/cm2
0.4
2
on, 100 mA/cm off
0.2
0.0
0 20 40 60 80 100
Time (h)
T = 248°C
8 mg Pt/cm2
2 m
Slurry deposit
• Integrated design
– Incorporate alcohol reforming
catalyst in anode chamber
0.8
hydrogen 0.3
0.6 reformate
1%CO
24%CO2 0.2
0.4 methanol
42 vol%
0.1
0.2
methanol
0.0 0.0
0.0 0.5 1.0 1.50.0
1.5 0.5 1.0 1.5
2
Current density (A/cm )
• Methanol power ~ 85% H2 power • Reformate power ~ 90% H2 power
• For polymer fuel cells ~ 10% • Methanol power ~ 45% H2 power
With reformer
T = 260 °C; 47 m membrane
ethanol
36 vol%
Vodka
80 proof
Component Materials
cathode (air electrode) (La,Sr)MnO3
Ni + YSZ composite
anode (fuel electrode)
(Ba0.5Sr0.5)(Co0.8Fe0.2)O2.3
• Traditional cathodes
– A3+B3+O3 perovskites
– Poor O2- transport
– Limited reaction sites
almost
• Our approach 1 in 4 vacant
– High O2- flux materials
– Extended reaction sites
– A2+B4+O3 perovskites
O2- O2-
electrolyte electrolyte
½ O2 +
2e -
O2,
• Symmetric cell Ar, O= Electrolyte
cathode
layers
resistance (CO2)
measurements 2e-
Ag current ½ O2
-
collectors
+
• Equivalent circuit Rcathode
– Distinguish resistance
contributions using Relectrolyte
frequency dependent
measurements Rcathode
-
750 700 650 600 550 500 450 400 fast O2- cathode
.cm )
2
10 10 O2-
electrolyte
P(O2) = 0.21 atm
Cathode area specific resistance (
electrolyte Porous
anode
anode
0.71 cm2
Anode: 700 m Electrolyte surface
~ 20m
1.3 cm
Electrolyte
Cathode: 20 m
2 m
-2
o
550 C
0.8 o
500 C
Voltage (Volts)
445 C 800
o
o
0.6 400 C
600
0.4
400
0.2 200
0.0 0
0 1000 2000 3000 4000
-2
Current density (mA.cm )
Comparison: literature cathode material 350 mW/cm2 at 600°C
Mary
Tetsuya
Justin
Wei
Calum Dane
Kenji
• The agencies
– National Science Foundation, Office of Naval Research,
DARPA, California Energy Commission, Department of
Energy, Kirsch Foundation, Powell Foundation
• S. M. Haile, “Fuel Cell Materials and Components,” (invited) Acta. Met. 51, 5981-
6000 (2003).
• S. M. Haile, “Materials for Fuel Cells,” (invited) Materials Today 18, 24-29 (2003).